Heterobimetallic Complexes of Rhenium and Zinc ... - ACS Publications

Apr 26, 2011 - -bipyridine (PNN) coordinates to rhenium carbonyls in both κ1(P) and κ2(N ... reaction and as potentially more selective homogeneous ...
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Heterobimetallic Complexes of Rhenium and Zinc: Potential Catalysts for Homogeneous Syngas Conversion Nathan M. West,† Jay A. Labinger,* and John E. Bercaw* Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125, United States

bS Supporting Information ABSTRACT:

6-(Diphenylphosphino)-2,20 -bipyridine (PNN) coordinates to rhenium carbonyls in both κ1(P) and κ2(N,N) modes; in the former, the free bpy moiety readily binds to zinc alkyls and halides. [Re(κ1(P)-PNN)(CO)5][OTf] reacts with dialkylzinc reagents to form [Re(κ1(P)-PNN 3 ZnR)(CO)4(μ2-C(O)R)][OTf] (R = Me, Et, Bn), in which an alkyl group has been transferred to a carbonyl carbon and the resulting monoalkyl Zn is bound both to the bpy nitrogens and the acyl oxygen. ZnCl2 binds readily to the bpy group in Re(κ1(P)-PNN)(CO)4Me, and the resulting adduct undergoes facile migratory insertion, assisted by the Lewis acidic pendent Zn, to yield Re(κ1(P)-PNN 3 ZnCl)(μ2-Cl)(CO)3(μ2-C(O)Me), in which one of the chlorides occupies the sixth coordination site on Re. Migratory insertion is inhibited by THF or other ethers that can coordinate to ZnCl2. Migratory insertion is also observed for Re(κ1(P)-PNN)(CO)4(CH2Ph) but not for Re(κ1(P)-PNN)(CO)4(CH2OCH3); coordination of the methoxy oxygen to Zn appears to block its ability to coordinate to the carbonyl oxygen and facilitate migratory insertion. Intramolecular Lewis acid promoted hydride transfer from [(dmpe)2PtH][PF6] to a carbonyl in [Re(κ1(P)-PNN)(CO)5][OTf] results in formation of a Reformyl species; additional hydride transfer leads to a novel ReZn-bonded product along with some formaldehyde.

’ INTRODUCTION The high volatility in the price of petroleum and forecasts of its decreasing availability have renewed interest in developing alternative approaches to fuel production. Conversion of methane- or coal-derived syngas (H2 þ CO) to liquids by the FischerTropsch reaction currently appears to offer the greatest promise,1 but the low selectivity of this heterogeneously catalyzed process is a drawback.2 Research on organometallic systems, both as mechanistic models for the FischerTropsch reaction and as potentially more selective homogeneous syngas conversion catalysts, has been active for several decades, but with only limited success, attributed in large part to the difficult formation of the first CH bond.3 Some anionic Ru carbonyl hydride reagents, similar to the active species for homogeneous CO hydrogenation, have been shown to reduce highly electrophilic metal carbonyls, such as [CpRe(CO)2(NO)]þ.3g,4 DuBois has introduced cationic group 9 and 10 transition metal hydrides that can be synthesized from H2 and are capable of transferring hydride to a broader range of metal carbonyls.5 We have recently shown that one of these hydridic reagents, in combination with a cationic manganese carbonyl complex, can effect the r 2011 American Chemical Society

(stoichiometric) reductive coupling of two CO molecules to a derivative of acetic acid.6 In a further elaboration, we synthesized rhenium carbonyl complexes containing ligands with a tethered borane and showed that the pendent Lewis acid facilitates the reductive coupling of two CO ligands;7 the borane, in combination with a strong base, can also function as a frustrated Lewis pair capable of cleaving dihydrogen and delivering a hydride to CO.7c These boron-linked complexes, while promising, do not appear viable for catalytic CO reduction, because the intermediate BO bonds are too strong to permit closing a cycle by releasing the organic product from the metal; a less oxophilic and more substitutionally labile Lewis acid that is still capable of promoting the desired reaction steps will be needed. In order to determine which Lewis acids might be suitable, we seek to develop versatile ligand architectures that can support the attachment of a variety of Lewis acidic metals in proximity to the ReCO reaction site. Our first candidate Received: January 20, 2011 Published: April 26, 2011 2690

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is 6-(diphenylphosphino)-2,20 -bipyridine (PNN), which is geometrically unlikely to act as a tridentate ligand to a single metal center; indeed, it has been shown to simultaneously bind two coppers, one at phosphorus and one through the nitrogens.8 We anticipated being able to attach the softer P center to a rhenium carbonyl species, leaving the bpy moiety available to bind a harder, Lewis acidic metal. We report here the synthesis of several such compounds, with zinc as the auxiliary metal, as well as the resulting facilitation of both migratory insertions and the transfer of a hydride to coordinated CO.

’ RESULTS AND DISCUSSION Re(PNN) Complexes. A phosphine-bound Re(PNN) complex can be readily obtained by heating Re(CO)5(OTf) with PNN at 50 C for 1 h (eq 1), yielding [Re(κ1(P)-PNN)(CO)5][OTf] (1), most clearly indicated by the 31P NMR shift from 3.7 ppm for free ligand to 12.2 ppm for the cationic Re complex. However, this coordination arrangement is not necessarily the most stable thermodynamically: refluxing Re(CO)5Br with PNN in toluene gives fac-Re(κ2(N,N)-PNN)(CO)3Br (2) (eq 2). Earlier results on related Re(PN-ligand) complexes9 suggest that the initial kinetic product might be cisRe(κ1(P)-PNN)(CO)4(Br) (3), followed by loss of CO and isomerization, so that 3 might be obtained under milder synthetic conditions. Indeed, treatment of the much more substitutionally labile [Re(CO)4(μ-Br)]2 with PPN at 50 C in CH2Cl2 for 1 h gives a roughly 2:1 mixture of 3 and 2 (eq 3). Pure 3 can be obtained by protonating PPN (at N) with triflic acid before reaction with [Re(CO)4(μ-Br)]2 at 60 C for 1 h, followed by deprotonation with alumina (eq 4). The structures of both 2 and 3 were confirmed by X-ray crystallography (Figure 1).

A methyl complex, cis-Re(κ1(P)-PNN)(CO)4(CH3) (4-Me), was obtained by heating Re(CO)5(CH3) with PNN at 110 C for 24 h (eq 5); there is no indication of either formation of an N,Ncoordinated species or any migratory insertion to give a rhenium acetyl complex. Clearly the binding preference of PNN is affected by the nature of other ligands; perhaps the more strongly donating methyl group renders the CO’s more substitutionally inert and makes the P-bound complex kinetically stable. The analogous alkyl complexes cis-Re(κ1(P)-PNN)(CO)4(CH2OCH3) (4-MOM) and cis-Re(κ1(P)-PNN)(CO)4(CH2Ph) (4-Bn) were prepared by reduction of 3 with Na/Hg, followed by treatment with ClCH2OCH3 or PhCH2Br, respectively (eq 6).

Formation of Zn-Stabilized Acyls by Alkyl Transfer. While addition of a main-group metal alkyl to MCO is a standard route for generating an acyl,10 no such reactions of alkyl Zn reagents with rhenium carbonyls appear to have been reported. Addition of ZnMe2 to a CD2Cl2 solution of 1 results in rapid formation of [Re(κ1(P)-PNN 3 ZnMe)(μ2-COMe)(CO)4][OTf] (5-Me), in which the Zn is bound to both the pendent bpy group and the oxygen of the newly formed acyl (eq 7). The 1 H NMR of 5-Me shows distinct signals for both the acetyl (2.45 ppm) and Zn (1.31 ppm) methyl groups, the 13C NMR spectrum includes a doublet (2JPC = 8 Hz) at 285.6 ppm for the acyl carbon, and the IR spectrum (CD2Cl2) displays peaks at 2100, 2018, and 1997 cm1 (terminal CO) as well as at 1534 cm1 (acyl CO). Similar treatment of 1 with ZnEt2 or ZnBn2 yields the analogous 5-Et and 5-Bn. All were isolated as sticky solids; no crystals could be obtained, despite multiple attempts. The methyl compound is stable in solution for several 2691

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Scheme 1

Figure 1. X-ray crystal structures of (top) fac-Re(κ2(N,N)-PNN)(CO)3Br (2) and (bottom) cis-Re(κ1(P)-PNN)(CO)4(Br) (3).

weeks, while the other two slowly decompose over the same period.

Addition of water removes the coordinated zinc and releases the free acyl compounds 6-Me, 6-Et, and 6-Bn. 6-Me exhibits IR peaks at 2087, 2000, 1978, and 1590 cm1. The modest but significant increase in the acyl CO stretching frequency (56 cm1) provides evidence that Zn is indeed coordinated to O in 5, but not so strongly that the interaction cannot be easily disrupted (in contrast to the strong BO bonds of the previously studied system), which is encouraging for the eventual

development of a catalytic system. Thermolysis of the neutral Re acyls 6 at ∼60 C leads to decarbonylation and formation of the corresponding Re alkyls 4 as the major products. In order to determine whether the proximity effect of the pendent bpy group plays a key role in this reaction, control reactions were performed on the simple triphenylphosphine analogue. No reaction was observed between [Re(PPh3)(CO)5][OTf] and excess ZnMe2 or ZnEt2 under similar conditions; however, addition of free bpy to a solution of [Re(PPh3)(CO)5][OTf] and ZnMe2 results in rapid formation of the known Re(PPh3)(COMe)(CO)4. The IR spectrum of Re(PPh3)(COMe)(CO)4 thus prepared is unaffected by water, with peaks (2088, 2000, 1976, and 1583 cm1) nearly identical with those of 6-Me, indicating that Zn does not remain coordinated to the acyl oxygen (Scheme 1).11 Apparently (bpy)ZnMe2 is a stronger methide transfer agent than ZnMe2 (good donor ligands have been shown to increase the reducing power of alkylzinc reagents12), which probably is primarily responsible for the facile reactions of 1 with ZnR2, rather than the attachment of the Zn-binding site to the Re center. ZnII-Facilitated Migratory Insertion. Migratory insertion for alkylrhenium carbonyls is rare; in addition to the B-centered Lewis acid promoted reactions mentioned earlier, there are only a few examples, all under forcing conditions.13 As noted above, reaction of Re(CO)5(CH3) with PNN at elevated temperature gives only CO replacement, not insertion; a similar reaction with PPh3 gives only Re(PPh3)(CO)4(CH3).14 Presumably this reluctance to undergo migratory insertion is a consequence of the strong MC bonds for the third-row metal Re; analogous Mn complexes undergo migratory insertion readily even at room temperature. A CH2Cl2-soluble form of ZnCl2 was obtained by dissolving ZnCl2 in THF and drying in vacuo, giving ZnCl2(THF) as a white powder.15 Addition of ZnCl2(THF) to a solution of 4-Me in CH2Cl2 rapidly gives a yellow species, whose 1H and 31P NMR spectra are only slightly altered, suggesting simple formation of the bpyZn adduct 7-Me. Over a few hours the doublet at 0.55 ppm for the Re methyl disappears and is replaced by a singlet at 2.27 ppm, in the expected region for an acyl methyl, suggesting insertion to form 8-Me (eq 8). The IR spectrum of this complex shows three peaks (at 2030, 1951, and 1896 cm1) as expected for a fac-tricarbonyl complex, but no obvious acyl CO stretch in the IR; probably it is obscured by bpy vibrations in the mid 1400 cm1 region (suggesting stronger bonding to Zn than in 5-Me). The structure of 8-Me was verified by X-ray crystallography; somewhat unexpectedly, Zn was found to be coordinated to only one N (the one further from P), the acyl oxygen, and both chlorides. One Cl occupies the Re site vacated by migratory insertion, forming a planar five-membered ring containing the Zn 2692

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Organometallics and Re (Figure 2). The Zn exhibits slightly distorted tetrahedral coordination; the free bpy N is only 2.7 Å away from Zn, but its pyridine ring is significantly rotated away from coplanarity with the coordinated pyr. The acyl CO bond distance of 1.253 Å is intermediate between typical values for Re acyls (∼1.21 Å)7a,10a,16 and Re alkoxycarbenes (∼1.31 Å),7a,17 which indicates significant weakening of the double bond due to coordination to Zn (as also suggested by the absence of a discernible IR stretch); this value is similar to those observed for other Lewis acid stabilized acyls.6,7a,7b,18 The conversion of 4-Me to 8-Me is analogous to other migratory insertions of group 7 alkyls facilitated by external Lewis acids AlX3 (X = Cl, Br),13a,18a,19 although ZnCl2 should be a considerably milder reagent than AlX3 (and hence potentially more compatible with catalysis).7b,13a,13c,13d,20 Indeed, in this system the intramolecular Lewis acid facilitation is essential: no reaction is observed between Re(PPh3)(CO)4(CH3) and either ZnCl2(THF) or Zn(bpy)Cl2. Even the (normally much more facile)21 insertion reaction for Mn(CO)5(CH3) was not effected by addition of ZnCl2(THF). Furthermore, cis-Re(κ1(P)2-(diphenylphosphino)pyridine)(CO)4(CH3), an analogue of

Figure 2. X-ray structure of 8-Me. Selected bond distances (Å) and angles (deg) for 8-Me: C4O4, 1.253(3); Zn2O4, 1.9475(19); Re1C4, 2.185(3); Re1Cl2, 2.5406(6); Zn2Cl2, 2.3023(7); Zn2Cl1, 2.2678(7); Zn2N1, 2.038(2); Re1CO(av), 1.938; Cl2Zn2O4, 99.78(6); Re1C4O4, 125.8(2); Zn2O4C4, 125.73(18); Cl2Re1C4, 88.81(7).

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4-Me with only a single “dangling” N center, shows no detectable insertion in the presence of ZnCl2(THF). It appears that bidentate coordination is required to bring the Zn into the secondary coordination sphere and initiate reaction; perhaps the steric bulk of the Re group then favors reversible dissociation of the proximal N, creating a vacant site on Zn that can interact with the CO oxygen and promote insertion.

The conversion of 7-Me to 8-Me in CH2Cl2 proceeds smoothly and cleanly, and the reaction may be followed by in situ IR or NMR spectroscopy, but the kinetics are not entirely straightforward. At low conversion, the reaction appears to be roughly first order in 7-Me, but the dependence on [ZnCl2(THF)] is more complex. The reaction is inhibited by excess THF and does not proceed at all in pure THF-d8, indicating an equilibrium between ZnCl2 3 4-Me (that is, 7-Me) and ZnCl2 3 THF, so that at high [THF], [7-Me] is very low, completely inhibiting reaction. Kinetics experiments with varying amounts of THF indicate an inverse order in THF between 1 and 2; the NMR behavior on titration of 4-Me with a 3:1 THF:ZnCl2 mixture is highly complex, suggesting the participation of multiple species depending on the concentration of THF, possibly as shown in Scheme 2. (In contrast, the NMR of 8-Me does not change significantly in THF.) Replacement of THF with Et2O or DME also led to complex inhibitory effects, and ZnCl2 cannot be used without any ether because of low solubility.

Scheme 2

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Organometallics While it is difficult or impossible to separate out individual rate and equilibrium constants for such a complex scheme, we can estimate a lower limit for the rate of the insertion step: a solution of 1 equiv of 4-Me and 10 equiv of a 3:1 mixture of THF and ZnCl2 smoothly converts to 8-Me with a pseudo-first-order rate constant of 4.0  105 s1 at 22 C. For comparison, the rate constant of migratory insertion for Re(CO)5Et in CH3CN (the only reported value) is 3.8  105 s1 at 46 C.13c While the numbers are similar, the difference in temperature, as well as the facts that the present value is a lower limit and migratory insertion is typically faster for Et than for Me groups,22 all imply significant acceleration by the pendent Zn Lewis acid. Reactions involving other Lewis acids and alkyl groups were also briefly investigated. Both ZnBr2/THF and ZnI2/THF promote formation of analogous insertion products; qualitatively the reaction is (slightly) fastest with ZnCl2 and slowest with ZnI2, as expected if the rate enhancement is dependent on Lewis acid strength. If the reaction were dependent on the nucleophilicity of the halide and its ability to bind to the Re, then the opposite trend might be expected. Addition of AgOTf to 4-Me gives no reaction, but addition of AgOTf to 7-Me results in rapid migratory insertion, suggesting this is caused by Ag removing Cl from Zn and generating a more Lewis acidic center. (Direct reaction of 4-Me with Zn(OTf)2 in CH2Cl2 is prohibited by insolubility.) This observation further supports the proposal that it is the binding of the carbonyl oxygen to the Zn, rather than coordination of the bridging Cl, that drives the reaction, with a transition state such as that shown in Figure 3. 4-Bn undergoes migratory insertion in the presence of ZnCl2(THF); the product exhibits two 1H NMR signals (4.20 and 3.71 ppm, 2JHH = 14.6 Hz) for the diastereotopic methylene protons that result from the conversion of Cs-symmetric 4-Bn to C1symmetric 8-Bn. This reaction is qualitatively slower than that of 4-Me, but the rates are within an order of magnitude. In previous studies on the (non Lewis acid assisted) migratory insertion of

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Mn alkyls, benzyl was the slowest to migrate, attributed to the electron-withdrawing nature of the phenyl group.22 In the same study the migration of CH2OMe was faster than that of benzyl; here, while 4-MOM rapidly forms an adduct with ZnCl2(THF), no further reaction is observed: 7-MOM persists over days or weeks in solution. The 1H NMR signal for the methylene protons of 7-MOM (which is not affected by added THF) is shifted considerably from that of 4-MOM upon reaction with Zn; no such shift is observed for the methyl and benzyl analogues. These results suggest that an interaction between O of the methoxymethyl ligand and Zn (eq 9) may interfere with the ability to facilitate migratory insertion.

8-Me is unaffected by washing with water, in contrast to the case for 5-Me, or by exposure to 1 atm of CO (in CD2Cl2 or THF-d8), in contrast to the case for acyl complexes formed with the aid of AlX3, where the bridging AlXM linkages are easily displaced by CO.13a,18a,19,23 Analogous Cl displacement by CO in 8-Me would lead to Re(κ1(P)-PNN 3 ZnCl2)(CO)4(COMe) (9-Me), which can be independently synthesized by addition of ZnCl2 to 6-Me; the acyl stretching frequency of 9-Me (1518 cm1) is 66 cm1 lower than that for 6-Me, indicating that the Zn is coordinated to the acyl oxygen (eq 10). Addition of water to 9-Me does result in facile removal of the Zn atom and regeneration of 6-Me. These observations suggest that the inertness of 8-Me under 1 atm of CO is due to kinetics, not thermodynamics.

Figure 3. Proposed transition state for Zn-promoted insertion.

Scheme 3

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Organometallics Reduction of Re Carbonyls with Hydride Reagents. Addition of ZnCl2(THF) to a CD2Cl2 solution of 1 gives ZnCl2 adduct 10, which upon addition of [(dmpe)2PtH][PF6] leads to immediate formation of a Re formyl complex, revealed by the appearance of a downfield 1H NMR signal (doublet at 15.06 ppm, 3JPH = 1 Hz); some H2 is also liberated. Initially formed in approximately 80% yield by NMR,24 the formyl species slowly decomposes over several days to give a red solution, which by NMR contains some regenerated 1 as well as a new species exhibiting a downfield 31P NMR shift (47.8 ppm), suggesting that P may be part of a five-membered ring. This compound was found by X-ray crystallography to have structure 11 (Scheme 3), a rare example (only the second structurally characterized25) of an organometallic complex containing a ReZn bond (Figure 4). The ReZn bond length of 2.61977(15) Å is about 0.07 Å shorter than those in [PPh4]2[Re7C(CO)21ZnCl].25b The Zn is coordinated to both N’s and has distorted-trigonal-

Figure 4. X-ray structure of Re(PNN 3 ZnCl)(CO)4 (11) (cocrystallized CH2Cl2 has been omitted for clarity). Selected bond distances (Å) and angles (deg): Re1Zn2, 2.61977(15); Re1P1, 2.4273(3); Re-CO(av), 1.960; Zn2N1, 2.1259(8); Zn2N2, 2.1158(8); Zn2Cl1, 2.3126(3); Re1Zn2N1, 139.93(2); Re1Zn2N2, 96.70(2); Re1ZnCl3, 125.978(8); N1ZnN2, 76.55(3).

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pyramidal geometry (the sum of angles around Zn is approximately 641; the theoretical values for trigonal-pyramidal and tetrahedral geometries are 630 and 657, respectively), in contrast to the Zn atom in 8-Me, which is coordinated to only one N and exhibits nearly tetrahedral geometry (sum of angles ∼654). The ZnCl distance of 2.3126(3) Å falls within the range observed for [NH4]2[ZnCl4] (2.112.40 Å).26 Reaction of 1 with Zn(OTf)2 and [(dmpe)2PtH][PF6] in CD3CN generates a complex closely analogous to 11 (indicated by the diagnostic downfield 31P NMR resonance) along with some H2, and a new 1H NMR singlet at 9.57 ppm, which corresponds well to the literature chemical shifts for formaldehyde in CD3CN.27 The latter signal disappears over a few hours with growth of a new singlet at 3.35 ppm, typical of a CH3OX species, which would be expected from the reaction of CH2O with unreacted PtH. The ReZn-bonded species, analogous to 11, might thus arise via sequential transfer of two hydrides to a CO, giving a zincoxymethyl group, which eliminates formaldehyde to generate the ReZn bond (Scheme 4). Such a sequence would be closely related to the known loss of formaldehyde from Re(CH2OH) to give ReH.27b It should be noted, however, that 11 is also formed on reaction of Re(κ1(P)-PNN)(CO)4(H) with ZnCl2; therefore, a route involving decarbonylation of the formyl group might account for some of the 11 formed by the reaction of Scheme 3. Presumably the stability of the ReZn bond allows formation of formaldehyde (which is highly thermodynamically disfavored), but it also appears to preclude catalytic reaction. Bright red 11 reacts rapidly with 1 equiv of Br2 in CD2Cl2 to cleave the ReZn bond and form light yellow Re(κ1(P)-PNN 3 Zn(Br)(Cl))(CO)4(Br) (12). Along with the color change, the 31P signal for the complex changes from 47.8 ppm for 11 to 10.4 ppm for 12; 10.4 ppm is nearly identical with the chemical shift for 3 þ ZnCl2(THF) and indicates that the five-membered ring containing phosphorus has been broken. Milder treatment of 11, such as exposure to an atmosphere of H2, does not result in any cleavage of the ReZn bond.

’ CONCLUSIONS Re(κ1(P)-PNN) carbonyl complexes constitute an effective structural framework for positioning a Lewis acidic Zn center to

Scheme 4

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Organometallics promote CO transformations that can play an essential role in the ultimate goal of homogeneous catalytic syngas conversion. The ZnII provides thermodynamic stabilization of the acyl species derived from either addition of alkylzinc reagents or migratory insertion, as well as accelerating the latter reaction, presumably by interacting with the carbonyl oxygen in the transition state. Migratory insertion is promoted only when the ZnII is intramolecularly anchored, not external. The formation of a formyl species by addition of PtH to ReCO may be promoted by the pendent Lewis acid (the analogous reaction of the simple phosphine complex [Re(CO)5(PPh3)]þ also yields a formyl, but one that is considerably less stable, decomposing over a period of hours instead of days7a,b), but the observation of formaldehyde demonstrates that under some conditions a second hydride transfer can be effected, a reaction that does not take place without Lewis acid promotion.7a,b These results show that the chelate effect makes it possible to facilitate difficult carbonylations by even relatively weak Lewis acids, such as Zn, that could be compatible with the requirements of a catalytic system. Ongoing work on this approach includes exploration of the behavior of other metals with the PNN ligand as well as development of additional supporting architectures.

’ EXPERIMENTAL SECTION Materials and Methods. All air- and moisture-sensitive compounds were manipulated using standard vacuum line or Schlenk techniques, or in a glovebox under a nitrogen atmosphere. The solvents for air- and moisture-sensitive reactions were dried with activated alumina by the method of Grubbs.28 All NMR solvents were purchased from Cambridge Isotopes Laboratories, Inc. Benzene-d6 was distilled from sodium benzophenone ketyl or titanocene. Dichloromethane-d2 and acetonitrile-d3 were distilled from calcium hydride and run through a small column of activated alumina. Tetrahydrofuran-d8 was purchased in a sealed ampule and dried by passage through activated alumina. Unless noted, other materials were used as received. Re(CO)5Br was purchased from Strem Chemicals, Inc. 6-Ph2P-2,20 -bpy (PNN),8a [Re(CO)4(μBr)]2,29 Re(CO)5OTf,30 and [HPt(dmpe)2][PF6]31 were synthesized according to literature procedures. Elemental analyses were performed by Robertson Microlit, Madison, NJ. 1H and 13C NMR spectra were recorded on Varian Mercury 300 MHz and Varian 400 MHz spectrometers at room temperature, unless indicated otherwise. Chemical shifts are reported with respect to residual internal protio solvent for 1H and 13 C{1H} spectra. 31P{1H} NMR spectra were referenced to external 85% H3PO4. X-ray crystallography was carried out by Dr. Michael W. Day and Lawrence M. Henling using a Bruker KAPPA APEXII X-ray diffractometer. [Re(K1(P)-PNN)(CO)5][OTf] (1). A solution of Re(CO)5(OTf) (140 mg, 0.295 mmol) and PNN (100 mg, 0.294 mmol) in 20 mL of CH2Cl2 was heated in a bomb to 50 C for 1 h. The solvent was removed in vacuo, and 10 mL of THF was added to the light yellow sticky product and evaporated in vacuo to remove any residual CH2Cl2. The solid was washed with 2  10 mL of THF to give a white powder (206 mg, 0.253 mmol, 86%). 1H NMR (300 MHz, CD2Cl2, δ, ppm): 8.75 (ddd, 1H, J = 4.8, 1.8, 1.0 Hz, 60 -bpy H); 8.66 (ddd, 1H, J = 8.1, 3.2, 1.0 Hz, 3-bpy H); 8.31 (dt, 1H, J = 8.0, 1.1 Hz, 50 -bpy H); 8.01 (td, 1H, J = 7.7, 1.8 Hz, 40 bpy H); 7.96 (td, 1H, J = 7.8, 4.0 Hz, 4-bpy H); 7.66 (m, 6H, Ph), 7.56 (m, 4H, Ph); 7.45 (ddd, 1H, J = 7.6, 4.8, 1.2 Hz, 30 -bpy H); 7.33 (ddd, 1H, J = 7.8, 3.5, 1.0 Hz, 5-bpy H). 31P{1H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 12.2 (s). 13C{1H} NMR (100.54 MHz, CD2Cl2, δ, ppm): 179.3 (br d, 4C, 2JPC = 7 Hz, cis-CO’s); 176.0 (br d, 1C, 2JPC = 39 Hz, trans-CO); 158.7 (d, 1C, 3JPC = 20 Hz, 2-bpy C); 154.4 (s, 1C, 20 -bpy C); 153.4 (d, 1JPC = 83 Hz, 6-bpy C); 150.3 (s, 1C, 60 -bpy C);

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139.3 (d, 1C, 3JPC = 7 Hz, 4-bpy C); 138.1 (s, 1C, 40 -bpy C); 133.4 (d, 2C, 4JPC = 3 Hz, p-Ph C); 133.0 (d, 4C, 2JPC = 11 Hz, o-Ph C); 130.6 (d, 4C, 3JPC = 11 Hz, m-Ph C); 129.4 (d, 2C, 1JPC = 52 Hz, i-Ph C); 128.7 (d, 1C, 2JPC = 18 Hz, 5-bpy C); 125.4 (s, 1C, 30 -bpy C); 125.1 (d, 1C, 4JPC = 2 Hz, 3-bpy C); 121.9 (s, 1C, 50 -bpy C); 121.6 (q, 1C, 1 JFC = 321 Hz, OTf C). IR (CH2Cl2, cm1): 2158 (s), 2055 (vs). Anal. Calcd for C28H17F3N2O8PReS: C, 41.23; H, 2.10; N, 3.43. Found: C, 41.44; H, 1.97; N, 3.36. Re(K2-PNN)(CO)3(Br) (2). PNN (100 mg, 0.294 mmol) was placed in a bomb containing solid Re(CO)5Br (120 mg, 0.295 mmol) and 20 mL of benzene. The mixture was heated overnight to 100 C, and the solvent was removed in vacuo to give the title compound as a bright yellow solid (649 mg, 0.276 mmol, 94%). Yellow needles suitable for X-ray structural analysis were grown by slow diffusion of pentane into a benzene solution of 2 at room temperature. 1H NMR (400 MHz, CD2Cl2, δ, ppm): 9.09 (d, 1H, J = 5 Hz), 8.23 (d, 1H, J = 8 Hz), 8.19 (d, 1H, J = 8.0 Hz), 8.06 (dt, 2H, J = 8, 1 Hz), 7.90 (t, 1H, J = 8 Hz), 7.87.7 (m, 5H, Ph, bpy), 7.57.3 (m, 8H, Ph, bpy). 31P{1H} NMR (162 MHz, CD2Cl2, δ, ppm): 5.7 (s). IR (Pet. Ether, cm1): 2020 (s), 1921 (s), 1896 (s). Anal. Calcd for C25H17BrN2O3PRe 3 C6H6: C, 48.44; H, 3.02; N, 3.64. Found: C, 48.28; H, 2.72; N, 3.63. Re(K1-PNN)(CO)4(Br) (3). PNN (100 mg, 0.294 mmol) was protonated with HOTf (26.0 μL, 44.1 mg, 0.294 mmol) in 10 mL of CH2Cl2, forming a yellow solution; after 5 min the solution was added to a bomb containing solid [Re(CO)4(μ-Br)]2 (112 mg, 0.148 mmol) and an additional 10 mL of CH2Cl2 was added. The mixture was heated to 60 C for 1 h. The solvent was removed in vacuo; the yellow residue was taken up in benzene, flushed through a plug of alumina, and dried in vacuo to give the title compound as an off-white powder (166 mg, 0.231 mmol, 79%). An X-ray-quality crystal was obtained as a large clear block (along with many yellow needles of 2 which formed over time) by slow diffusion of pentane into a benzene solution of 3 . 1H NMR (400 MHz, CD2Cl2, δ, ppm): 8.69 (dd, 1H, J = 4.0, 0.7 Hz, 60 -bpy), 8.50 (ddd, 1H, J = 8.1, 2.6, 0.8 Hz, 5-bpy), 8.38 (d, 1H, J = 8.0 Hz, 50 -bpy), 7.83 (tt, 2H, J = 7.9, 2.6 Hz, 4,40 -bpy), 7.787.68 (m, 4H, Ph), 7.637.41 (m, 6H, Ph), 7.36 (ddd, 1H, J = 7.5, 4.7, 1.1 Hz, 3 or 30 -bpy), 7.24 (ddd, 1H, J = 7.7, 3.4, 0.8 Hz, 3 or 30 -bpy). 31P{1H} NMR (162 MHz, CD2Cl2, δ, ppm): 5.4 (s). IR (petroleum ether, cm1): 2106 (m), 2020 (s), 2003 (s), 1951 (m). Anal. Calcd for C26H17BrN2O4PRe 3 CH2Cl2: C, 40.36; H, 2.38; N, 3.49. Found: C, 40.57; H, 2.37; N, 3.54. Re(PNN)(CO)4(Me) (4-Me). PNN (100 mg, 0.294 mmol) and Re(CO)5(CH3) (100 mg, 0.293 mmol) were placed in a bomb and dissolved in 20 mL of toluene. The bomb was heated to 120 C for 24 h. The solvent was removed under vacuum, and the resulting dark oily product was extracted several times with ∼20 mL of hexanes. The hexanes were removed under vacuum to give 8-Me as a sticky oil (65 mg, 0.100 mmol, 34%). Alternatively, reduction of 3 (200 mg, 0.290 mmol) with Na/Hg (33.0 mg of Na/3.3 g of Hg, 1.17 mmol) and methylation with MeI (36 μL, 82 mg, 0.580 mmol) gives 4-Me (121 mg, 0.186 mmol, 64%), as does thermolysis of 6-Me (80 mg, 0.117) at 100 C in benzene (20 mL) overnight (54 mg, 68%). 1H NMR (300 MHz, CD2Cl2, δ, ppm): 8.67 (ddd, 1H, J = 4.8, 1.8, 0.9 Hz, bpy H); 8.47 (ddd, 1H, J = 8.0, 2.5, 1.0 Hz, bpy H); 8.41 (td, 1H, J = 8.0, 1.1 Hz, bpy H); 7.83 (ddd, 1H, J = 8.0, 7.2, 1.8 Hz, bpy H); 7.80 (td, 1H, J = 7.9, 3.6 Hz, bpy H); 7.59 (m, 4H, Ph); 7.47 (m, 6H, Ph); 7.35 (ddd, 1H, J = 7.5, 4.8, 1.2 Hz, bpy H); 7.22 (ddd, 1H, J = 7.7, 3.5, 1.0 Hz, bpy H); 0.53 (d, 3JPH = 7.7 Hz, 3H, ReCH3). 31P{1H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 12.5 (s). Anal. Calcd for C27H20N2O4PRe: C, 49.61; H, 3.08; N, 4.29. Found: C, 51.02; H, 3.63; N, 3.97. Re(PNN)(CO)4(CH2OMe) (4-MOM). In the glovebox, compound 3 (250 mg, 0.362 mmol) was dissolved in 15 mL of THF and added dropwise to a flask containing a 1% Na/Hg amalgam (40.5 mg of Na/4.1 g of Hg, 1.45 mmol). The solution turned dark purple after stirring for 4 h. The solution was decanted from the Na/Hg into a flask containing 2696

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Organometallics ClCH2OCH3 (41.2 μL, 0.543 mmol) dissolved in 10 mL of THF. Immediately the solution lightened in color and a cloudy precipitate formed. After it was stirred overnight, the solution was evaporated; the residue was taken up in 15 mL of benzene and filtered through a plug of silica gel. The benzene was then evaporated, leaving 4-MOM as a clear oil (52 mg, 0.079 mmol, 0.22%). Solid, analytically pure samples could not be obtained. 1H NMR (300 MHz, CD2Cl2, δ, ppm): 8.66 (d, 1H, J = 4.5 Hz, bpy H); 8.47 (dd, 1H, J = 7.7, 2.0 Hz, bpy H); 8.41 (d, 1H, J = 8.4 Hz, bpy H); 7.81 (m, 2H, bpy H); 7.67.5 (m, 4H, Ph); 7.49 (m, 6H, Ph); 7.34 (dd, 1H, J = 7.5, 5.1 Hz, bpy H); 7.25 (dd, 1H, J = 7.5, 3.3 Hz, bpy H); 3.72 (d, 2H, J = 6.0 Hz, CH2OCH3); 2.94 (s, 3H, CH2OCH3). 31 1 P{ H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 14.4 (s). IR (ν, cm1, hexanes): 2085, 1993, 1978, 1941. Re(PNN)(CO)4(Bn) (4-Bn). A procedure analogous to that for 4MOM was used, with PhCH2Br (64.6 μL, 0.543 mmol) instead of ClCH2OCH3. 4-Bn was isolated as a light brown oil (113 mg, 0.161 mmol, 45%). Alternatively, 6-Bn (45 mg, 0.062 mmol) could be heated to 80 C overnight in 15 mL of benzene to yield crude 4-Bn, which can be purified by flushing the solution through a plug of silica (32 mg, 0.046 mmol, 71%). Solid, analytically pure samples could not be obtained. 1H NMR (300 MHz, CD2Cl2, δ, ppm): 8.69 (ddd, 1H, J = 4.8, 1.8, 0.9 Hz, bpy H); 8.51 (ddd, 1H, J = 8.0, 2.5, 1.0 Hz, bpy H); 8.48 (td, 1H, J = 8.0, 1.0 Hz, bpy H); 7.86 (dt, 1H, J = 7.8, 1.8 Hz, bpy H); 7.83 (td, 1H, J = 7.9, 3.6 Hz, bpy H); 7.66 (m, 4H, Ph); 7.52 (m, 6H, Ph); 7.37 (ddd, 1H, J = 7.6, 4.8, 1.2 Hz, bpy H); 7.23 (ddd, 1H, J = 7.7, 3.4, 1.0 Hz, bpy H); 6.98 (m, 1H, Bn H); 6.76 (dd, 2H, J = 8.2, 1.2 Hz, Bn H); 6.68 (t, 2H, J = 7.3 Hz, Bn H); 1.94 (d, 3JPH = 6.1 Hz, 3H, ReCH2Ph). 31P{1H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 13.4 (s). Re(Ph2Ppy)(CO)4(Me). A procedure analogous to the synthesis of 4-Me was used, but with Ph2Ppy (77 mg, 0.294 mmol) instead of PNN. The reaction was much cleaner than the PNN reaction and gave 152 mg (0.252 mmol, 86% yield) of white powder. 1H NMR (300 MHz, CD2Cl2, δ, ppm): 8.72 (d, 1H, J = 4.8 Hz, 6-H, py); 7.77.3 (m, 13H, Ph, py); 0.5 (d, 3H, J = 7 Hz, ReCH3). 31P{1H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 9.8 (s). IR (CH2Cl2, cm1): 2075, 2091, 1969, 1930. [Re(PNN 3 ZnMe)(CO)4(COMe)][OTf] (5-Me). To a CD2Cl2 solution (0.6 mL) of 1 (15 mg, 0.018 mmol) in a J. Young NMR tube was added 1 drop of ZnMe2. The tube was capped and shaken; the reaction was quantitatively complete by the time the 1H NMR spectrum could be recorded. Removal of the solvent from the reaction by vacuum and trituration with 5 mL of pentane yielded 5-Me as a sticky clear oil (16 mg, 0.018 mmol, 100%). 1H NMR (300 MHz, CD2Cl2, δ, ppm): 8.77 (dd, 1H, J = 8.3, 1.1 Hz, 3-bpy H); 8.70 (m, 2H, 50 ,60 -bpy H); 8.36 (td, 1H, J = 7.8, 1.8 Hz, 40 -bpy H); 8.30 (td, 1H, J = 8.2, 2.6 Hz, 4-bpy H); 7.82 (ddd, 1H, J = 7.7, 5.0, 1.0 Hz, 30 -bpy H); 7.62 (m, 6H, Ph); 7.48 (m, 4H, Ph); 7.27 (ddd, 1H, J = 7.9, 5.0, 0.9 Hz, 5-bpy H); 2.45 (s, 3H, ReCOCH3); 1.31 (s, 3H, ZnCH3). 31P{1H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 9.4 (s). 13C{1H} NMR (100.54 MHz, CD2Cl2, δ, ppm): 283.1 (br s, 1C, C(OZn)CH3); 188.2 (br s, 2C, cis-P-cis-COMeCO’s); 186.0 (d, 1C, 2JPC = 9 Hz, cis-P-trans-COMe-CO); 185.0 (d, 1C, 2JPC = 45 Hz, trans-P-trans-COMe-CO); 156.7 (d, 1C, 1JPC = 56 Hz, 6-bpy C); 153.4 (d, 3JPC = 10 Hz, 2-bpy C); 149.6 (s, 1C, 20 -bpy C); 148.9 (s, 1C, 60 -bpy C); 143.0 (d, 1C, 3JPC = 6 Hz, 4-bpy C); 142.8 (s, 1C, 40 -bpy C); 134.5 (d, 4C, 2JPC = 11 Hz, o-Ph C); 133.4 (d, 2C, 4 JPC = 2 Hz, p-Ph C); 131.5 (d, 1C, 2JPC = 15 Hz, 5-bpy C); 130.7 (d, 4C, 3JPC = 11 Hz, m-Ph C); 121.1 (br d, 2C, 1JPC = 48 Hz, i-Ph C); 128.4 (s, 1C, 30 -bpy C); 125.5 (d, 1C, 4JPC = 1 Hz, 3-bpy C); 124.6 (s, 1C, 50 -bpy C); 121.3 (q, 1C, 1JFC = 321 Hz, OTf C); 57.6 (s, 1C, C(OZn)CH3); 15.0 (br s, 1C, ZnCH3). IR (CH2Cl2, cm1): 2100 (m), 2018 (s), 1997 (s), 1535 (w). Anal. Calcd for C30H23F3N2O8PReSZn: C, 39.55; H, 2.54; N, 3.07. Found: C, 39.27; H, 2.43; N, 2.97. [Re(PNN 3 ZnEt)(CO)4(COEt)][OTf] (5-Et). The same procedure as for 5-Me was used, but with ZnEt2 (1 drop); formation of 5-Et was

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quantitative by 1H NMR. 1H NMR (500 MHz, CD2Cl2, δ, ppm): 8.77 (m, 3H, 3,50 ,60 -bpy H); 8.37 (m, 1H, 40 -bpy H); 8.31 (td, 1H, J = 8.1, 2.6 Hz, 40 -bpy H); 7.83 (ddd, 1H, J = 7.6, 5.1, 1.0 Hz, 30 -bpy H); 7.62 (m, 6H, Ph); 7.47 (m, 4H, Ph); 7.29 (ddd, 1H, J = 7.8, 4.9, 0.9 Hz, 5-bpy H); 2.76 (q, 2H, 3JHH = 7.1 Hz, ReCOCH2CH3); 0.87 (t, 3H, 3JHH = 8.1 Hz, ZnCH2CH3); 0.32 (t, 3H, 3JHH = 7.1 Hz, ReCOCH2CH3); 0.55 (q, 2H, 3JHH = 7.1 Hz, ZnCH2CH3). 31P{1H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 9.9 (s). 13C{1H} NMR (125.71 MHz, CD2Cl2, δ, ppm): 285.8 (d, 1C, 2JPC = 8 Hz, C(OZn)CH2CH3); 186.1 (d, 1C, 2 JPC = 8 Hz, cis-P-trans-COEt-CO); 185.2 (d, 1C, 2JPC = 45 Hz, transP-trans-COEt-CO); 156.9 (d, 1C, 1JPC = 56 Hz, 6-bpy C); 153.5 (d, 3 JPC = 11 Hz, 2-bpy C); 149.7 (s, 1C, 20 -bpy C); 149.2 (s, 1C, 60 -bpy C); 143.1 (d, 1C, 3JPC = 6 Hz, 4-bpy C); 142.7 (s, 1C, 40 -bpy C); 134.4 (d, 4C, 2JPC = 11 Hz, o-Ph C); 133.4 (d, 2C, 4JPC = 2 Hz, p-Ph C); 131.5 (d, 1C, 2JPC = 15 Hz, 5-bpy C); 130.7 (d, 4C, 3JPC = 11 Hz, mPh C); 128.2 (s, 1C, 30 -bpy C); 125.6 (s, 1C, 3-bpy C); 124.8 (s, 1C, 50 bpy C); 63.1 (s, 1C, C(OZn)CH2CH3); 12.9 (s, 1C, ZnCH2CH3); 8.4 (s, 1C, C(OZn)CH2CH3); 0.182 (s, 1C, ZnCH2CH3). [Re(PNN 3 ZnEt)(CO)4(COBn)][OTf] (5-Bn). The same procedure as for 5-Me was used, but with ZnBn2 (1 drop); formation of 5Bn was quantitative by 1H NMR. ZnBn2 was formed by stirring ZnCl2 (100 mg, 0.733 mmol) and KBn (191 mg, 1.47 mmol) in 10 mL of benzene for 30 min and then filtering the solution through Celite and removing the solvent under vacuum. 1H NMR (300 MHz, CD2Cl2, δ, ppm): 8.45 (m, 2H, bpy H); 8.7 (m, 2H, 4,40 -bpy H); 7.65 (m, 6H, Ph); 7.52 (m, 4H, Ph); 7.31 (m, 2H, bpy H); 7.16.7 (m, 9H, Ph); 6.47 (d, 2H, o-Bn); 4.03 (br s, 2H, ReCOCH2Ph); 1.91 (br s, 2H, ZnCH2Ph). 31 1 P{ H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 10.8 (s). Re(PNN)(CO)4(COMe) (6-Me). A CD2Cl2 solution of 5-Me, prepared as described above, was washed with 10 mL of water in air and dried over MgSO4. After filtration the CH2Cl2 was removed in vacuo to yield 6-Me (11 mg, 0.016 mmol, 90%). 1H NMR (300 MHz, CD2Cl2, δ, ppm): 8.68 (ddd, 1H, J = 4.8, 1.8, 1.0 Hz, bpy H); 8.49 (ddd, 1H, J = 8.0, 2.7, 1.0 Hz, bpy H); 8.41 (td, 1H, J = 8.0, 1.1 Hz, bpy H); 7.82 (m, 2H, bpy H); 7.62 (m, 6H, Ph); 7.49 (m, 4H, Ph); 7.35 (ddd, 1H, J = 4.8, 2.7, 1.1 Hz, bpy H); 7.24 (ddd, 1H, J = 4.3, 3.4, 1.1 Hz, bpy H); 2.16 (s, 3H, ReCOCH3). 31P{1H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 13.8 (s). 13C{1H} NMR (100.54 MHz, CD2Cl2, δ, ppm): 257.5 (d, 1C, 2 JPC = 10 Hz, C(O)CH3); 190.2 (d, 2C, 2JPC = 10 Hz, cis-P-cisCOMe-CO’s); 189.3 (d, 1C, 2JPC = 46 Hz, trans-P-trans-COMe-CO); 189.1 (d, 1C, 2JPC = 7 Hz, cis-P-trans-COMe-CO); 158.0 (d, 1C, 1 JPC = 74 Hz, 6-bpy C); 157.3 (d, 3JPC = 17 Hz, 2-bpy C); 155.5 (s, 1C, 20 -bpy C); 149.8 (s, 1C, 60 -bpy C); 137.8 (d, 1C, 3JPC = 6 Hz, 4-bpy C); 137.5 (s, 1C, 40 bpy C); 134.3 (d, 4C, 2JPC = 11 Hz, o-Ph C); 133.1 (br d, 2C, 1JPC = 47 Hz, i-Ph C); 131.5 (d, 2C, 4JPC = 2 Hz, p-Ph C); 129.2 (d, 4C, 3JPC = 10 Hz, m-Ph C); 128.1 (d, 1C, 2JPC = 18 Hz, 5-bpy C); 124.8 (s, 1C, 30 -bpy C); 122.3 (d, 1C, 4JPC = 2 Hz, 3-bpy C); 122.0 (s, 1C, 50 -bpy C); 56.4 (d, 1C, 3JPC = 1 Hz, C(O)CH3). IR (petroleum ether, cm1): 2087 (m), 1997 (s), 1978 (s), 1952 (s). Re(PNN)(CO)4(COEt) (6-Et). The same procedure as for 6-Me was used, but with 5-Et (10 mg, 0.016 mmol, 80%). 1H NMR (300 MHz, C6D6, δ, ppm): 8.61 (td, 1H, J = 8.0, 1.1 Hz, bpy H); 8.55 (ddd, 1H, J = 7.9, 2.7, 1.0 Hz, bpy H); 8.47 (ddd, 1H, J = 4.8, 1.8, 0.9 Hz, bpy H); 7.72 (m, 4H, bpy H, Ph); 7.24 (td, 1H, J = 7.7, 1.8 Hz, bpy H); 7.16.9 (m, 8H, Ph); 6.66 (ddd, 1H, J = 7.6, 4.8, 1.6 Hz, bpy H); 2.64 (q, 3JHH = 7.3 Hz, 2H, ReCOCH2CH3); 0.76 (t, 3JHH = 7.3 Hz, 3H, ReCOCH2CH3). 31 1 P{ H} NMR (121.5 MHz, C6D6, δ, ppm): 13.1 (s). IR (petroleum ether, cm1): 2084 (m), 1993 (s), 1975 (s), 1948 (s). Re(PNN)(CO)4(COBn) (6-Bn). The same procedure as for 6-Me was used, but with 5-Bn (12 mg, 0.016 mmol, 88%). 1H NMR (300 MHz, CD2Cl2, δ, ppm): 8.69 (d, 1H, J = 4.2 Hz, bpy H); 8.51 (d, 1H, J = 8.0 Hz, bpy H); 8.43 (d, 1H, J = 8.0 Hz, bpy H); 7.83 (m, 2H, bpy H); 7.63 (m, 6H, Ph); 7.49 (m, 4H, Ph, Bn H); 7.36 (m, 2H, Hz, bpy H, Bn H); 7.26 (dd, 1H, J = 7.4, 3.0 Hz, bpy H); 7.16 (m, 2H, Bn H); 6.80 (d, 2697

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Organometallics 2H, J = 6.6 Hz, Bn H); 3.75 (s, 3H, ReCOCH2Ph). 31P{1H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 13.2 (s). Re(PPh3)(CO)4(COMe). To a CD2Cl2 solution (0.6 mL) of [Re(PPh3)(CO)5][OTf] (15 mg, 0.020 mmol) and 2,20 -bipyridine (4.0 mg, 0.026 mmol) in a J. Young NMR tube was added 1 drop of ZnMe2. The tube was capped and shaken; the resulting 1H NMR spectrum showed quantitative conversion to the acyl. The sample can be washed with water in air in a manner analogous to the preparation of 6; the resulting product is a mixture of Re(PPh3)(CO)4(COMe) and 2,20 bipyridine by 1H NMR. 1H NMR (300 MHz, CD2Cl2, δ, ppm): 8.70 (d, 3H, J = 4.8 Hz, Ph); 8.29 (d, 3H, J = 8.1 Hz, Ph); 8.14 (td, 3H, J = 7.9, 1.6 Hz, Ph); 7.64 (dd, 3H, J = 7.1, 5.6 Hz, Ph); 7.47 (m, 3H, Ph); 2.28 (s, 3H, ReCOCH3). 31P NMR (121.5 MHz, CD2Cl2, δ, ppm): 9.6 (s).

Re(PNN 3 ZnCl2)(CO)4(Me) (7-Me) and Re(PNN 3 Zn(Cl)(μCl))(CO)3(COMe) (8-Me). Solid ZnCl2(THF) (4.0 mg, 0.019 mmol) was added to a CD2Cl2 solution (0.6 mL) of 4-Me (12.4 mg, 0.0190 mmol) in an NMR tube which was capped and shaken, giving a yellow solution of 7-Me, which was not isolated but was observed in situ. 1H NMR (300 MHz, CD2Cl2, δ, ppm): 8.69 (d, 1H, J = 4.1 Hz, 60 -bpy H); 8.36 (d, 1H, J = 7.0 Hz, bpy H); 8.29 (d, 1H, J = 8.0 Hz, bpy H); 8.04 (m, 2H, bpy H); 7.67 (m, 4H, Ph); 7.53 (m, 8H, Ph, bpy H); 0.55 (d, 3H, 3 JPH = 7.5 Hz, ReCH3). 31P{1H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 13.3 (s). Some chemical shifts are dependent on the concentration of THF in solution. IR (CH2Cl2, cm1): 2078, 2018, 1945. Over the course of several hours 7-Me smoothly underwent migratory insertion to form 8-Me, which was isolated by pouring the solution into a vial and drying in vacuo (15 mg, 0.019 mmol, 100%). Small X-rayquality crystals were obtained by slow diffusion of pentane into a CH2Cl2 solution. 1H NMR (300 MHz, CD2Cl2, δ, ppm): 9.73 (d, 1H, J = 5 Hz, 60 -bpy H); 8.25 (m, 1H, bpy H); 8.14 (d, 1H, J = 8 Hz, bpy H); 7.99 (d, 1H, J = 8 Hz, bpy H); 7.92 (td, 1H, J = 8 Hz, 2 Hz, bpy H); 7.82 (m, 1H, bpy H); 7.62 (m, 3H, Ph); 7.43 (m, 7H, Ph); 2.26 (s, 3H, Re(COCH3)). 31P{1H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 16.8 (s). IR (CH2Cl2, cm1): 2030 (s), 1952 (s), 1896 (s), 1492 (m), 1435 (m). 13C{1H} NMR (100.54 MHz, CD2Cl2, δ, ppm): 309.8 (s, 1C, C(OZn)CH3); 196.5 (s, 1C, CO’s); 192.7 (s, 1C, CO’s); 192.2 (s, 1C, CO’s); 159.2 (d, 1C, 1JPC = 58 Hz, 6-bpy C); 152.4 (d, 3JPC = 13 Hz, 2-bpy C); 152.1 (s, 1C, 20 -bpy C); 151.9 (s, 1C, 60 -bpy C); 143.0 (s, 1C, 40 -bpy C); 141.0 (s, 1C, 4-bpy C); 134.4 (d, 4C, 2JPC = 11 Hz, o-Ph C); 133.2 (d, 4C, 3JPC = 11 Hz, m-Ph C); 131.8 (d, 2C, 1JPC = 49 Hz, i-Ph C); 127.5 (s, 1C, 30 -bpy C); 124.9 (s, 1C, 3-bpy C); 124.3 (s, 1C, 50 -bpy C); 129.5 (m, 3C, p-Ph C, 5-bpy C); 52.8 (s, 1C, C(OZn)CH3). Re(PNN 3 Zn(Cl)(μ-Cl))(CO)3(COBn) (8-Bn). 4-Bn (10.5 mg, 0.0144 mmol) and ZnCl2(THF) (3.0 mg, 0.014 mmol) were combined by the same procedure as for 8-Me; 8-Bn was not isolated. 1H NMR (300 MHz, CD2Cl2, δ, ppm): 9.27 (d, 1H, J = 4.6 Hz, 60 -bpy H); 8.43 (t, 2H, J = 8.2, bpy H); 8.36 (m, 2H, bpy H); 8.11 (d, 1H, J = 8.0, 1.8 Hz, bpy H); 7.62 (m, 4H, Ph); 7.49 (m, 6H, Ph); 7.28 (m, 1H, Ph); 7.16 (m, 2H, Ph); 6.93 (dd, 2H, J = 7.8, 1.7, Bn H); 4.20 (d, 1H, J = 14.6 Hz, Re(COCH2Ph)); 3.71 (d, 1H, J = 14.6 Hz, Re(COCH2Ph)). 31P{1H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 16.1 (s).

Reaction of Re(PNN)(CO)4(CH2OMe) (4-MOM) with ZnCl2(THF). 4-MOM (12.8 mg, 0.0187 mmol) and ZnCl2(THF) (4.0 mg, 0.019 mmol) were combined by the same procedure as for 8-Me. 7MOM forms rapidly and can be observed by 1H NMR (400 MHz, C2D2Cl4, δ, ppm): 9.48 (br s, 1H, 60 -bpy H); 8.15 (m, 1H, bpy H); 7.84 (br m, 2H); 7.52 (m, 12H), 7.25 (br d, 1H, J = 6 Hz, bpy H); 4.81 (br s, 2H, CH2OCH3); 2.90 (br s, 3H, CH2OCH3). Continued monitoring of the sample shows no change, indicating that migratory insertion does not occur. Evaporating the solvent from the NMR tube and redissolving in THF-free CD2Cl2 results in no significant change in the chemical shifts of 7-MOM. 7-MOM was not isolated. Re(PNN 3 ZnCl2)(CO)4(COMe) (9). To a CD2Cl2 solution (0.6 mL) of 6-Me (15 mg, 0.022 mmol) was added ZnCl2(THF) (5.0 mg,

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0.024 mmol); the solution was shaken and transferred to a J. Young NMR tube. Compound 9 was the only species present in solution by the time the first NMR spectrum could be taken; 9 was not isolated but was observed in situ. A small amount of the solution was transferred to a solution IR cell in the glovebox, and the IR was recorded. Washing the solution of 9 with 10 mL of water resulted in the removal of Zn and reformation of 6-Me, as observed by IR. 1H NMR (400 MHz, CD2Cl2, δ, ppm): 8.90 (d, 1H, J = 5.0 Hz, bpy H); 8.68 (dd, 1H, J = 8.0, 1.8 Hz, bpy H); 8.63 (d, 1H, J = 8.1 Hz, bpy H); 8.45 (td, 2H, J = 8.0, 2.9 Hz, bpy H); 7.85 (dt, 1H, J = 7.3, 5.6 Hz, bpy H); 7.61 (m, 7H, Ph, bpy H); 7.47 (m, 4H, Ph); 2.75 (s, 3H, ReCOCH3). 31P{1H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 13.4 (s). 13C{1H} NMR (100.54 MHz, CD2Cl2, δ, ppm): 294.1 (s, 1C, C(OZn)CH3); 187.4 (d, 2C, J = 9 Hz, cis-P-cis-COMe-CO’s); 186.1 (d, 1C, 2JPC = 7 Hz, cis-P-trans-COMe-CO); 185.0 (d, 1C, 2JPC = 45 Hz, trans-P-trans-COMe-CO); 157.3 (d, 1C, 1JPC = 58 Hz, 6-bpy C); 153.4 (d, 3JPC = 13 Hz, 2-bpy C); 150.1 (s, 1C, 20 -bpy C); 149.7 (s, 1C, 60 -bpy C); 143.7 (br s, 2C, 40 ,4-bpy C); 134.5 (d, 4C, 2JPC = 11 Hz, o-Ph C); 133.5 (s, 2C, p-Ph C); 131.9 (d, 1C, 2JPC = 14 Hz, 5-bpy C); 130.7 (d, 4C, 3 JPC = 11 Hz, m-Ph C); 129.6 (d, 2C, 1JPC = 49 Hz, i-Ph C); 128.8 (s, 1C, 30 -bpy C); 126.4 (s, 1C, 3-bpy C); 125.6 (s, 1C, 50 -bpy C); 58.0 (s, 1C, C(OZn)CH3). IR (CD2Cl2, cm1): 2103, 2023, 1998, 1971, 1518. [Re(PNN 3 ZnCl2)(CO)5][OTf] (10). Solid ZnCl2(THF) (4.0 mg, 0.019 mmol) and 1 (15 mg, 0.018 mmol) were combined in a vial and dissolved in CD2Cl2 (0.6 mL), and the solution was transferred to a J. Young NMR tube, yielding 10, which was observed in situ. 1H NMR (300 MHz, CD2Cl2, δ, ppm): 9.00 (ddd, 1H, J = 5.3, 1.6, 0.8 Hz, 60 bpy H); 8.40 (ddd, 1H, J = 7.9, 3.3, 0.9 Hz, bpy H); 8.21 (td, 1H, J = 7.8, 1.6 Hz, bpy H); 8.05 (d, 1H, J = 7.7 Hz, bpy H); 8.01 (td, 1H, J = 7.9, 3.9 Hz, bpy H); 7.62 (m, 11H, Ph, bpy H); 7.39 (ddd, 1H, J = 7.9, 3.5, 0.9 Hz, bpy H). 31 1 P{ H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 13.8 (s). Some chemical shifts are dependent on the concentration of THF in solution. Reaction of 10 with [(dmpe)2PtH][PF6]. To a CD2Cl2 solution (0.6 mL) of 10 in an NMR tube was added [(dmpe)2PtH][PF6] (12 mg, 0.018 mmol); the NMR showed the formation of some H2 and 1 in addition to formation of Re(PNN 3 ZnCl)(CO)4 (11) in increasing amounts as the amount of PtH used was increased. (Alternatively, 11 was obtained from the reaction of CD3CN solution (0.6 mL) of 1 (15 mg, 0.018 mmol) and Zn(OTf)2 (7.0 mg, 0.019 mmol) with [(dmpe)2PtH][PF6].) After several days X-ray-quality orange crystals of 11 formed in the bottom of the NMR tube. Characterization data for 11 are as follows. 1H NMR (300 MHz, CD2Cl2, δ, ppm): 8.98 (ddd, 1H, J = 5.1, 1.6, 0.9 Hz, 60 -bpy H); 8.28 (dt, 1H, J = 8.1, 1.1 Hz, bpy H); 8.19 (dd, 1H, J = 7.6, 1.7 Hz, bpy H); 8.14 (ddd, 1H, J = 8.0, 2.5, 0.8 Hz, bpy H); 7.96 (td, 1H, J = 7.8, 2.5 Hz, bpy H); 7.74 (ddd, 1H, J = 7.5, 1.5, 1.2 Hz, bpy H); 7.48 (m, 10H, Ph); 7.33 (ddd, 1H, J = 7.7, 2.0, 0.7 Hz, bpy H). 31P{1H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 47.8 (s). Anal. Calcd for C26H17Cl1N2O4PReZn 3 CH2Cl2: C, 39.34; H, 2.32; N, 3.40. Found: C, 39.11; H, 2.51; N, 3.32. Re(PNN 3 Zn(Br)(Cl))(CO)4(Br) (12) in Situ from 11. To a CD2Cl2 (0.6 mL) slurry of several crystals of 11 in an NMR tube was added 1 drop of Br2, and the tube was shaken to yield an orange solution (the product is yellow; the solution was tinted orange by unreacted Br2) of 12. 1H NMR (300 MHz, CD2Cl2, δ, ppm): 8.86 (d, 1H, J = 4.7 Hz, 60 bpy H); 8.49 (m, 2H, bpy H); 8.29 (m, 1H, bpy H); 8.16 (td, 1H, J = 8.2, 2.6 Hz, bpy H); 7.69 (m, 4H, Ph); 7.59 (m, 7H, Ph, bpy H); 7.48 (dd, 1H, J = 7.4, 3.8 Hz, bpy H). 31P{1H} NMR (121.5 MHz, CD2Cl2, δ, ppm): 10.4 (s). NMR Kinetics. Because 4-Me and 4-Bn could not be isolated as solids, standard solutions of the reagents were used: a sample of 4 was dissolved in a measured amount of C2D2Cl4 along with a known amount of a standard, such as ferrocene, a measured volume aliquot of the solution was removed and diluted with C2D2Cl4, and the 1H NMR spectrum was recorded. From this the molarity of the solution could be determined by comparison of the integrals of 4 to those of the standard. 2698

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Organometallics A standard solution of 3:1 THF:ZnCl2 in C2D2Cl4 was also prepared. The solution of 4 was combined with 10 equiv (based on Zn) of the Zn solution and additional THF as needed in a J. Young NMR tube and then diluted to a total volume of 0.8 mL with C2D2Cl4. The reaction progress was monitored by 1H NMR spectroscopy. Kinetics experiments using ZnCl2(DME) (DME = 1,2-dimethoxyethane), ZnBr2(THF), and ZnI2(THF) instead of ZnCl2(THF) were also conducted using the same procedure. ZnCl2(THF). Anhydrous ZnCl2 (500 mg, 3.66 mmol) was dissolved in 10 mL of dry THF, and the solvent was evaporated after all of the ZnCl2 had dissolved. After it was dried under vacuum for 1 h, the vial was weighed; 769 mg of white powdery contents were obtained (100.1% yield based on ZnCl2(THF)). X-ray-quality clear hygroscopic needles were grown from CH2Cl2/pentane, but data collection was stopped when the preliminary structure was found to be the same as that published for [Zn(Cl)(μ-Cl)(THF)]¥.15a

’ ASSOCIATED CONTENT

bS

Supporting Information. CIF files, figures, and tables giving crystal structure data for 2, 3, 8-Me, and 11. This material is available free of charge via the Internet at http://pubs.acs.org. Crystallographic data have also been deposited at the CCDC, 12 Union Road, Cambridge CB2 1EZ, U.K., and copies can be obtained on request, free of charge, by quoting the publication citation and the deposition numbers 793163 (2), 793162 (3), 757498 (8-Me), an 757305 (11).

’ AUTHOR INFORMATION Corresponding Author

*E-mail: [email protected] (J.A.L.); [email protected] (J.E.B.). Present Addresses †

Department of Chemistry and Biochemistry, University of the Sciences, 600 S 43rd St., Philadelphia, PA 19104.

’ ACKNOWLEDGMENT We acknowledge Larry Henling and Dr. Mike Day for their assistance with crystallography, Dr. David VanderVelde for his assistance with NMR spectroscopy, Alex Miller for helpful discussions, and the continued generous financial support of BP through the MC2 program. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (No. CHE-0639094). ’ REFERENCES (1) (a) Khodakov, A. Y.; Chu, W.; Fongarland, P. Chem. Rev. 2007, 107, 1692. (b) Rofer-DePoorter, C. K. Chem. Rev. 1981, 81, 447. (2) United Nations Development Program. World Energy Assessment Report: Energy and the Challenge of Sustainability; United Nations: New York, 2000. (3) (a) Maitlis, P. M. J. Mol. Catal. A 2003, 204205, 55. (b) Maitlis, P. M.; Zanotti, V. Chem. Commun. 2009, 1619. (c) Cutler, A. R.; Hanna, P. K.; Vites, J. C. Chem. Rev. 1988, 88, 1363. (d) Marko, L. Transition Met. Chem. 1992, 17, 474. (e) Marko, L. Transition Met. Chem. 1992, 17, 587. (f) West, N. M.; Miller, A. J. M.; Labinger, J. A.; Bercaw, J. E. Coord. Chem. Rev. 2011, 255, 881–898. (g) Barratt, D. S.; ColeHamilton, D. J. J. Organomet. Chem. 1986, 306, C41. (h) Ishino, M.; Tamura, M.; Deguchi, T.; Nakamura, S. J. Catal. 1992, 133, 325. (i) Ishino, M.; Tamura, M.; Deguchi, T.; Nakamura, S. J. Catal. 1992, 133, 332.

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(4) (a) Dombek, B. D.; Harrison, A. M. J. Am. Chem. Soc. 1983, 105, 2485. (b) Barratt, D. S.; Cole-Hamilton, D. J. J. Chem. Soc., Chem. Commun. 1985, 1559. (c) Barratt, D. S.; Glidewell, C.; Cole-Hamilton, D. J. J. Chem. Soc., Dalton Trans. 1988, 1079. (5) (a) Miedaner, A.; DuBois, D. L.; Curtis, C. J.; Haltiwanger, R. C. Organometallics 1993, 12, 299. (b) Curtis, C. J.; Miedaner, A.; Ellis, W. W.; DuBois, D. L. J. Am. Chem. Soc. 2002, 124, 1918. (c) Wilson, A. D.; Miller, A. J. M.; DuBois, D. L.; Labinger, J. A.; Bercaw, J. E. Inorg. Chem. 2010, 49, 3918. (6) Elowe, P. R.; West, N. M.; Labinger, J. A.; Bercaw, J. E. Organometallics 2009, 28, 6218. (7) (a) Miller, A. J. M.; Labinger, J. A.; Bercaw, J. E. Organometallics 2010, 29, 4499. (b) Miller, A. J. M.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 2008, 130, 11874. (c) Miller, A. J. M.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 2010, 132, 3301. (8) (a) Field, J. S.; Haines, R. J.; Parry, C. J.; Sookraj, S. H. S. Afr. J. Chem. 1993, 46, 70. (b) Field, J. S.; Haines, R. J.; Parry, C. J.; Sookraj, S. H. Polyhedron 1993, 12, 2425. (c) Field, J. S.; Haines, R. J.; Warwick, B.; Zulu, M. M. Polyhedron 1996, 15, 3741. (9) (a) Hoyano, J.; Peterson, L. K. Can. J. Chem. 1976, 54, 2697. (b) Cobbledick, R. E.; Dowdell, L. R. J.; Einstein, F. W. B.; Hoyano, J. K.; Peterson, L. K. Can. J. Chem. 1979, 57, 2285. (c) Anaya, S. A. S.; Hagenbach, A.; Abram, U. Polyhedron 2008, 27, 3587. (10) (a) Goldberg, K. I.; Bergman, R. G. J. Am. Chem. Soc. 1989, 111, 1285. (b) Reinartz, S.; White, P. S.; Brookhart, M.; Templeton, J. L. Organometallics 2002, 21, 247. (c) Cross, J. L.; Crane, T. W.; White, P. S.; Templeton, J. L. Organometallics 2003, 22, 548. (11) Attempts to use a catalytic amount of bpy to facilitate the transfer failed. This suggests that that Zn(Me)(OTf) and ZnMe2 do not readily exchange bpy ligands. (12) (a) Hevia, E.; Kennedy, A. R.; Klett, J.; Livingstone, Z.; McCall, M. D. Dalton Trans. 2010, 39, 520. (b) Kobayashi, K.; Kondo, Y. Org. Lett. 2009, 11, 2035. (13) (a) Lindner, E.; Vonau, G. Angew. Chem. 1980, 19, 824. (b) Casey, C. P.; Jones, W. D. J. Am. Chem. Soc. 1980, 102, 6154. (c) Martin, B. D.; Warner, K. E.; Norton, J. R. J. Am. Chem. Soc. 1986, 108, 33. (d) Warner, K. E.; Norton, J. R. Organometallics 1985, 4, 2150. (14) Andersen, J.-A. M.; Moss, J. R. J. Organomet. Chem. 1995, 494, 105. (15) (a) Bottomley, F.; Ferris, E. C.; White, P. S. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 1989, C45, 816. (b) Dashti, A.; Niediek, K.; Werner, B.; Neumuller, B. Z. Anorg. Allg. Chem. 1997, 623, 394. (16) Goldberg, K. I.; Bergman, R. G. Organometallics 1987, 6, 430. (17) (a) Casey, C. P.; Czerwinski, C. J.; Fusie, K. A.; Hayashi, R. K. J. Am. Chem. Soc. 1997, 119, 3971. (b) Haupt, H.-J.; Petters, D.; Florke, U. J. Organomet. Chem. 1998, 558, 81. (18) (a) Butts, S. B.; Strauss, S. H.; Holt, E. M.; Stimson, R. E.; Alcock, N. W.; Shriver, D. F. J. Am. Chem. Soc. 1980, 102, 5093. (b) Llewellyn, S. A.; Green, M. L. H.; Cowley, A. R. Dalton Trans. 2006, 1776. (19) Butts, S. B.; Holt, E. M.; Strauss, S. H.; Alcock, N. W.; Stimson, R. E.; Shriver, D. F. J. Am. Chem. Soc. 1979, 101, 5864. (20) McKinney, R. J.; Kaesz, H. D. J. Am. Chem. Soc. 1975, 97, 3066. (21) Calderazzo, F.; Cotton, F. A. Inorg. Chem. 1962, 1, 30. (22) Cawse, J. N.; Fiato, R. A.; Pruett, R. L. J. Organomet. Chem. 1979, 172, 405. (23) Richmond, T. G.; Basolo, F.; Shriver, D. F. Inorg. Chem. 1982, 21, 1272. (24) Approximately 10% formation of ReH is observed as well (5.12 ppm, d, 22 Hz); yields were determined by comparison of integrals to the THF signal. (25) (a) Mays, M. J.; Hsieh, A. T. T. J. Chem. Soc. A 1971, 2648. (b) Wright, C. A.; Shapley, J. R. Inorg. Chem. 2001, 40, 6338. (26) Mikhail, I. Acta Crystallogr. 1980, B36, 2126. (27) (a) Integrated Spectral Database System of Organic Compounds, 2011, WHPM02816. (b) Gibson, D. H.; Sleadd, B. A.; Yin, X. L.; Vij, A. Organometallics 1998, 17, 2689. 2699

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Organometallics

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(28) Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics 1996, 15, 1518. (29) (a) Abel, E. W.; Hargreaves, G. B.; Wilkinson, G. J. Chem. Soc. 1958, 3149. (b) Sohmit, S. P.; Trogler, W. C.; Basolo, F. Inorg. Synth. 1985, 23, 41. (c) Dolcetti, G.; Norton, J. R. Inorg. Synth. 1976, 16, 35. (30) Schmidt, S. P.; Nitschke, J.; Trogler, W. C.; Huckett, S. I.; Angelici, R. J. Inorg. Synth. 1989, 26, 113. (31) Miedaner, A.; DuBois, D. L.; Curtis, C. J.; Haltiwanger, R. C. Organometallics 1993, 12, 299.

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